CN115353651A - Carbon nano tube and cellulose composite film and preparation method thereof - Google Patents
Carbon nano tube and cellulose composite film and preparation method thereof Download PDFInfo
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- CN115353651A CN115353651A CN202210841365.1A CN202210841365A CN115353651A CN 115353651 A CN115353651 A CN 115353651A CN 202210841365 A CN202210841365 A CN 202210841365A CN 115353651 A CN115353651 A CN 115353651A
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 78
- 239000001913 cellulose Substances 0.000 title claims abstract description 78
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 39
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 49
- 239000013078 crystal Substances 0.000 claims abstract description 24
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 229920001046 Nanocellulose Polymers 0.000 claims abstract description 9
- 238000000967 suction filtration Methods 0.000 claims abstract description 7
- 239000006185 dispersion Substances 0.000 claims abstract description 5
- 238000003825 pressing Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 6
- 238000007731 hot pressing Methods 0.000 claims description 4
- 239000002121 nanofiber Substances 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 3
- 238000007710 freezing Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 229920000742 Cotton Polymers 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 238000010008 shearing Methods 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 4
- 238000000034 method Methods 0.000 abstract description 5
- 238000007711 solidification Methods 0.000 abstract 1
- 230000008023 solidification Effects 0.000 abstract 1
- 239000007900 aqueous suspension Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
A carbon nano tube and cellulose composite film and a preparation method thereof relate to the carbon nano tube composite material technology, in particular to a carbon nano tube reinforced cellulose base composite film preparation technology. According to the invention, the composite film contains 95-98% of cellulose by mass; the film is prepared by dispersing carbon nanotubes in a nano cellulose crystal aqueous solution to obtain a first solution, mixing the first solution and a cellulose solution to obtain a second solution, carrying out suction filtration on the second solution, and then pressing a film. The preparation method of the film comprises four procedures of cellulose solution preparation, carbon nano tube dispersion and mixing, film preparation, solidification and the like, and is characterized in that the carbon nano tube and the cellulose solution are mixed by taking the water solution of nano cellulose crystal as a medium. The prepared composite film has high mechanical property and electric conduction property.
Description
Technical Field
The invention relates to a carbon nano tube composite material technology, in particular to a carbon nano tube reinforced cellulose base composite film preparation technology.
Background
The carbon nano tube has excellent mechanical and electrical properties, and the nano polymer composite film prepared by using the carbon nano tube as the filler has both mechanical and electrical properties, and is widely researched at present. The functional film has wide application prospect, such as wearable electronic devices, super capacitors and the like. The technical difficulty in preparing composite materials from carbon nanotubes is to disperse the carbon nanotubes uniformly in the matrix material.
Cellulose is a natural polymer material widely existing in plant bodies, and the technology of extracting nanofiber crystals from plant fibers has been industrially applied. The nanocellulose crystals are usually present in the form of an aqueous suspension, which is a green dispersion of carbon nanotubes due to nano-adsorption and hydrogen bonding, which can be uniformly dispersed in the aqueous nanocellulose crystal suspension and remain stable for a long time. Meanwhile, as the nano-cellulose crystal is a structural form of cellulose and the solvents of the two solutions are aqueous solutions, the nano-cellulose crystal aqueous suspension can be conveniently mixed with the cellulose aqueous solution.
Disclosure of Invention
The invention provides a carbon nanotube reinforced cellulose-based composite film and a preparation method thereof, which have the advantages of simple process, environmental protection, low manufacturing cost and the like, and provide a new way for developing and preparing green functional films.
The carbon nanotube and cellulose composite film is characterized in that the cellulose content in the composite film is 95-98% by mass;
the film is prepared by dispersing carbon nanotubes in a nano cellulose crystal aqueous solution to obtain a first solution, mixing the first solution and a cellulose solution to obtain a second solution, carrying out suction filtration on the second solution, and then pressing a film.
The cellulose in the cellulose solution is natural cellulose, cotton linter, paper pulp or cellulose crystal particles, and the polymerization degree is 300-800.
The nano-cellulose crystal aqueous solution dispersed with the carbon nano-tubes is dropwise added into a natural cellulose solution, and high-speed shearing or ultrasonic dispersion mixing is carried out simultaneously.
The natural cellulose is dissolved in a mixed aqueous solution of sodium hydroxide and urea.
The preparation method of the carbon nano tube and cellulose composite film is characterized by comprising the following steps:
step 1, according to the mass ratio, sodium hydroxide: urea: deionized water =8-12: 5-9: 79-87 to prepare a solution;
step 2, adding natural cellulose into the solution obtained in the step 1, and fully stirring and uniformly mixing, wherein the content of the cellulose is 1-4% by mass;
step 3, freezing the mixed solution of the cellulose, the sodium hydroxide, the urea and the deionized water obtained in the step 2 for 10-60min in an environment of-10 to-14 ℃;
step 4, fully stirring and mixing the mixed solution obtained in the step 3 until the natural cellulose is fully dissolved to obtain a cellulose solution;
step 5, adding the carbon nano tube into the nanofiber crystal aqueous solution, and then performing dispersion mixing to obtain a first solution;
step 6, dropwise adding the first solution obtained in the step 5 into the cellulose solution obtained in the step 4, and carrying out rapid stirring or strong ultrasonic treatment to uniformly mix the two solutions to obtain a second solution;
step 7, carrying out vacuum auxiliary suction filtration treatment on the second solution obtained in the step 6 to prepare a film, and then washing the film with deionized water until the washing liquid is neutral;
and 8, carrying out hot pressing treatment on the film obtained in the step 7 on a hot press to obtain the carbon nano tube and cellulose composite film.
The invention utilizes the characteristic that the nano-crystalline cellulose water suspension can be used as a dispersing agent of the carbon nano-tube and is compatible with the cellulose aqueous solution, and the carbon nano-tube is uniformly dispersed into the cellulose aqueous solution, thereby providing possibility for preparing the carbon nano-tube filled cellulose base composite material. And (3) uniformly dispersing the carbon nano tubes in the cellulose aqueous solution by using the nano-cellulose crystal water suspension as a dispersion medium to obtain the cellulose aqueous solution with uniformly dispersed carbon nano tubes.
The invention utilizes nano-cellulose crystal water suspension as a dispersion medium, uniformly disperses the carbon nano-tubes in the cellulose water solution, and combines the suction filtration and hot pressing processes to prepare the carbon nano-tube/cellulose composite film, has the advantages of simple process, environment-friendly process, low manufacturing cost and the like, and provides a new way for developing and preparing green functional films.
Drawings
FIG. 1 shows the film prepared in example 1.
FIG. 2 is a film prepared in example 2.
FIG. 3 is a schematic view of the structure of the film obtained by the present invention, wherein (a) is a top view and (b) is a front view.
Detailed Description
Example 1: the preparation method of the carbon nano tube and cellulose composite film comprises the following specific steps:
step 1, preparing sodium hydroxide according to mass ratio: urea: deionized water = 12.
And 2, adding the natural cellulose into the solution obtained in the step 1, and fully stirring and uniformly mixing, wherein the content of the natural cellulose is 2% by mass.
And 3, freezing the mixed solution of the natural cellulose, the sodium hydroxide, the urea and the deionized water obtained in the step 2 for 30min at the temperature of-12 ℃.
And 4, fully stirring the mixed solution obtained in the step 3 until the natural cellulose is fully dissolved to obtain the natural cellulose solution.
And 5, taking 20ml of nano-fiber crystal deionized water solution with the mass fraction of 1%, adding a proper amount of hydroxylated carbon nano-tubes into the nano-cellulose crystal water solution, then carrying out dispersion and mixing to obtain the nano-cellulose crystal water solution with uniformly dispersed carbon nano-tubes, and adjusting the concentration of the mixed solution by using deionized water to ensure that the mass of the hydroxylated carbon nano-tubes accounts for 3% and the mass of the nano-cellulose crystals accounts for 1%.
And 6, dropwise adding the nano-cellulose crystal aqueous solution obtained in the step 5 into the natural cellulose solution obtained in the step 4, rapidly stirring, and carrying out ultrasonic treatment for 5min to uniformly mix the two solutions.
And 7, carrying out suction filtration on the mixed solution obtained in the step 6 to prepare a film, and then washing with deionized water until the washing liquid is neutral.
And 8, carrying out hot pressing treatment on the film obtained in the step 7 on a hot press to obtain the carbon nano tube and cellulose composite film.
FIG. 1 is a schematic diagram of a film obtained in this example. The detection shows that the conductivity of the composite film is 1.5 +/-0.2S/m, and the test shows that the film has good flexibility and can be repeatedly folded without being damaged.
FIG. 3 is a schematic view of the structure of the composite film obtained in this example. The composite film is composed of three components, namely a cellulose substrate which is a basic component of the film and has the function of bonding and compounding the carbon nano tube and the nano cellulose crystal into an integral structure to form the film; the carbon nano tube plays a role in strengthening and conducting the film; and thirdly, the nano cellulose crystal plays a role in strengthening the film.
Example 2: in the step 5, the mass fraction of the nano-crystalline cellulose is 2%, the mass fraction of the hydroxylated carbon nano-tube is 4.5%, and the mass fraction of the nano-crystalline cellulose is 1.5%; the other steps are the same as in example 1.
FIG. 2 is a schematic view of the film obtained in this example. The detection shows that the conductivity of the composite film is 2.2 +/-0.2S/m, and the film has good flexibility and can be repeatedly folded.
Claims (5)
1. The carbon nano tube and cellulose composite film is characterized in that the cellulose content in the composite film is 95-98% by mass;
the film is prepared by dispersing carbon nanotubes in a nano cellulose crystal aqueous solution to obtain a first solution, mixing the first solution and a cellulose solution to obtain a second solution, carrying out suction filtration on the second solution, and then pressing a film.
2. The carbon nanotube-cellulose composite film according to claim 1, wherein the cellulose in the cellulose solution is natural cellulose, cotton linter, pulp, or cellulose crystal particles, and the degree of polymerization is 300 to 800.
3. The carbon nanotube-cellulose composite film according to claim 1, wherein the carbon nanotube-dispersed nanocellulose crystal aqueous solution is added dropwise to a natural cellulose solution while being subjected to high-speed shearing or ultrasonic dispersion mixing.
4. The carbon nanotube-cellulose composite film according to claim 1, wherein the natural cellulose is dissolved in a mixed aqueous solution of sodium hydroxide and urea.
5. The preparation method of the carbon nano tube and cellulose composite film is characterized by comprising the following steps:
step 1, according to the mass ratio, sodium hydroxide: urea: deionized water =8-12: 5-9: 79-87 to prepare a solution;
step 2, adding natural cellulose into the solution obtained in the step 1, and fully stirring and uniformly mixing, wherein the content of the cellulose is 1-4% by mass;
step 3, freezing the mixed solution of the cellulose, the sodium hydroxide, the urea and the deionized water obtained in the step 2 for 10-60min in an environment with the temperature of-14 to-10 ℃;
step 4, fully stirring and mixing the mixed solution obtained in the step 3 until the natural cellulose is fully dissolved to obtain a cellulose solution;
step 5, adding the carbon nano tube into the nanofiber crystal aqueous solution, and then performing dispersion mixing to obtain a first solution;
step 6, dropwise adding the first solution obtained in the step 5 into the cellulose solution obtained in the step 4, and carrying out rapid stirring or strong ultrasonic treatment to uniformly mix the two solutions to obtain a second solution;
step 7, carrying out vacuum auxiliary suction filtration treatment on the second solution obtained in the step 6 to prepare a film, and then washing the film with deionized water until the washing liquid is neutral;
and 8, carrying out hot pressing treatment on the film obtained in the step 7 on a hot press to obtain the carbon nano tube and cellulose composite film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210841365.1A CN115353651A (en) | 2022-07-18 | 2022-07-18 | Carbon nano tube and cellulose composite film and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210841365.1A CN115353651A (en) | 2022-07-18 | 2022-07-18 | Carbon nano tube and cellulose composite film and preparation method thereof |
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| Publication Number | Publication Date |
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| CN115353651A true CN115353651A (en) | 2022-11-18 |
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| CN202210841365.1A Pending CN115353651A (en) | 2022-07-18 | 2022-07-18 | Carbon nano tube and cellulose composite film and preparation method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080284054A1 (en) * | 2006-04-21 | 2008-11-20 | Jiangsu Long-Ma Green Fibers Co., Ltd. | Use of Aqueous Naoh/Thiourea Solution in Pilot-Scale Production of Cellulose Products |
| CN111647196A (en) * | 2020-04-24 | 2020-09-11 | 南京林业大学 | Preparation method of wood-based carbon nanotube composite conductive film |
-
2022
- 2022-07-18 CN CN202210841365.1A patent/CN115353651A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080284054A1 (en) * | 2006-04-21 | 2008-11-20 | Jiangsu Long-Ma Green Fibers Co., Ltd. | Use of Aqueous Naoh/Thiourea Solution in Pilot-Scale Production of Cellulose Products |
| CN111647196A (en) * | 2020-04-24 | 2020-09-11 | 南京林业大学 | Preparation method of wood-based carbon nanotube composite conductive film |
Non-Patent Citations (2)
| Title |
|---|
| HUA-DONG HUANG等: "Simultaneous Reinforcement and Toughening of Carbon Nanotube/Cellulose Conductive Nanocomposite Films by Interfacial Hydrogen Bonding", 《ACS SUSTAINABLE CHEMISTRY & ENGINEERING》, pages 317 - 324 * |
| 张少博: "木材纤维素修饰碳纳米管增强纤维素基复合材料研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》, pages 014 - 117 * |
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Application publication date: 20221118 |